Manufacture of an acrylic acid ester



Patented June 3, 1952 STATES PATENT OF CE MANUFACTURE OF AN ACRYLIC ACID ESTER.

No Drawings Original rnlicaticn Fcb qerr 1948, Serial No. 7,998, Diyide and, th' li cation June 19, 1950, S erial hl Switzerland February 21,1341

' 10 Claims. 1

This application is a division of abandoned ernl catioascr- Ncflfi-QS. filed, ifebruary 12,19,5 8-

According, to his int nt on esters or defin carhoxyliq acids ar made. y r a n cempound. Q ithc a etylene. seri s w th. n cke arbonylor cqhal carb ny i h. h add ti nfoi an id ndi oifa hyd tqx c pqund whichcon ain at least, one. a coholic. y sr ro p an a least one, carbon chain with at least 12 carbon om n hi mann r ther re ob ained rom compounds containing the grouping C'EC-- esters containing the; grouping Q o=.cso* 4 l W llfib e -2B: E QE EI E 5 1% 3 53 59 i h? hydroxy compound; ha ng; t formu a rionlormixtcrcs o suchan te w thth free olefinecaibma'lic acid. Withacetylenethere are Qb aircd l! th s nrcc s s ct a r l c acid mixtures 011 ry ic acid st rs and; free, cr li acid. I As, a compound of the, acetylene-series acetylen itself is the preferred, starting material. How;- ever. theremay also be usedas starting materials substituted acetylenes, such, as methylracetylene, ethyl-acetylene, phenyl-acetylene, vinyl-acetylene, divinyl-acetylene, isopropenyl-acetylene, 1- ethinyl cyclohexene-(lb; and also alkinols or alkine-diols such as butine-(l) 01 -(4), pentene- (3)--ine('1)-ol-(5), and also ethers or' esters thereof or products obtainable therefrom by deydration; fu hermore ketcn sci t e c ne series, such as hexene-(S) -ine-()-one-(2); also propiolic acid esters or other acetylene carboxylic acid esters, such as stearolic acid esters, dehydr -un ecylenic a id st rs, ndeco c ci esters, behenolic acid esters. There are also to be mentioned among acetylene compounds which may be used as starting materials alkinols derived from sterqid k on s c a t stosterone. o fr m te ralones. y th add tion. Q acetyle e- Amo g; the hy oxy c m ounds. wh ch conta n atleast one alcoholichydroigy groupand at, least one carbon chain with at least 12 carbon atoms to be used as starting, materials in the invention there may emerltio ed the io lcwins a ho a m l ohcl r wl al ene l ctadecyl. al h lmontan' alc hol; furt er he llq lns h rc yl compounds: Hydroxy-carbozgylic acids such as ricinoleic acid or the hydroxy-stearic acid obtainable by the hydrogenation 0i r qinoleic acid; esters and amides of hydroxy-carboxylic acids, such as yl s yco atemethyl ricirlcleate,

'octadecyl; ricinoleate, castoroil, ll-hydroxy stearic acid; c'etyl ester, Il-hydrdxwstearic acid amide; polyhydric alcohols partiallyl esteriiied with carboir'ylic acids, especially higher fatty acids, such as'lauric acid B-hydroxy-ethyl ester, stearic acid fl hydroxyethy-l ester, be he1ii c acid fl-hydroxyethyl ester, montanic acidpl-hydroxy ethyl ester; monoor diglycerides of higher fatty acids, for example, of; stearic acid, oleic: acid, linoleic acid or linolenic acid, such as'linseed oil fatty" acid monogl ycer-ide or linseed oil iatty acid. diglyceride; hydroxyalkyl amides of higher'iatty acids, such 'as stearic acid B-hydroxyethylainide; further hydroxy-alkyl-thioethe1 ssuch as c-hydroxy-ethyl-dodecyl thioether.

There may be used as acids in the present invention, for example, hydrohalic acids; especially hydrochloric acid, butalso phosphoric acidor aceticacid; They are advantageously usedin aqueous solution. t

The reaction; oithe invention may. becarried out by mixing] the reactants together at room temperature or at a raised temperature, if desired, in a pressure vessel. When acetylene and nickel carbonyl amused as-starting materials the reaction maybe carried'out at'room temperature or a moderately raised temperature, for example,-

at 30-80 0; under atmospheric-pressureor under superatmoispheric pressure. For example, acetylenemaybe introduced into a mixture ofglthe hydrox-ycompound; and the acid and the niclgel carbonyl introduced dropwiseat the same time. It is still more advantageous to mix the hydroiiy compound, acid and nickel carbonyl together, if desired, with the addition of a solvent} preferably an inert one, and to agitate the miggture with acetylene in a suitable agitating rider S h s n m nhc ie P es re Su t tu e ece es lower reacts/4c: tremb e nols; are advantageously reacted withthle' ne al carbonyl, especially nickel carbonyl, at a raised temperature, for example, at 50-120" C., the use of he asi olatile iche! ca b n l makin it 5 am to. Work i a pressure ss t V F r t e p1 P9 world s n er atmqs c 1. pressure, 1;, ea ersed M l 'm-ol f time com ound a least 4 mol of niclg l carbonyl. qr cobalt c shew Eli-least V m o 1 acid and at least 1 mol of the hyd, ne n n. he re c c s we us pressure vessel at a raised temperature,

when the latter is conducted at a raised temperature and under pressure, by working in the presence of metallic nickel or cobalt or a salt thereof, especially a halide, with the addition of an excess of carbon monoxide. In this case only small quantities of nickel or cobalt or a salt thereof are necessary, as these additions act as catalysts.

The process may be conducted discontinuously or continuously.

As already stated the products of the invention consist predominantly of esters of carboxylic acids which contain a double bond in the (1:5- position, if desired, in admixture with the carboxylic acids from which the esters are derived. When necessary, the free oleflne carboxylic acids present in the reaction mixture may be subsequently esterified. This may be brought about in the usual manner, for example, by distilling off the water present in the reaction mixture, and heating the mixture containing the olefine carboxylic acid and the alcohol until the esterification ceases. The water may be removed during the esterification azeotropically or, in the case of high boiling alcohols, by evacuation.

Owing to the reactive double bond the products of the invention are suitable, for example, as intermediate products, for instance, for the manufacture of polymerisates. The acrylic acid esters obtainable, for example, from acetylene, polymerise with the application of heat, especially in the presence of a polymerisationaccelerator, such as benzoyl peroxide, whereby polymerisates are obtanied whose properties depend on the choice of the starting materials.

Such polymeric acrylic acid esters can be used for producing coatings on textiles or paper, and also as artificial substances or adhesives or as constituents of lacquers, artificial masses or the like. Acrylic acid esters obtained by the invention and containing an aliphatic residue of at least 16 carbon atoms can be used, either in monomeric or polymeric form, for improving textiles, especially for dressing them and imparting hydrophobic properties thereto. To this end the textiles may, for example, be impregnated with solutions of the polymeric ester in organic solvents or with aqueous dispersions thereof, and

dried at a raised temperature. Alternatively, suitable monomeric acrylic acid esters, especially those which polymerize easily, may be applied to the textile material, and polymerized on the fiber at a raised temperature in the presence of a substance which accelerates the polymerisation.

The following examples illustrate the invention, the parts being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example 1 74 parts of hardened castor oil are dissolved with heat in a mixture of 135 parts of benzene and 115 parts of benzine. The warm solution, after the addition of 18 parts of concentrated hydrochloric acid (density=1.199) and parts of nickel carbonyl, is agitated with acetylene until the gas is no longer absorbed. At the outset the color changes towards dark brown, and as the reaction proceeds the color becomes pale again and solid NiClz separates, while there is a considerable spontaneous liberation of heat.

After cooling, the whole is filtered to remove the precipitated nickel chloride, and the solvent 4 is removed by distillation under reduced pressure.

There are obtained parts of. the triacrylic acid ester of the hydrogenated castor oil, which is easily soluble in most solvents. The chief constituent of the new ester corresponds to the formula By heating it on the water-bath in the presence of a small quantity of benzoyl peroxide (for example, 0.1 per cent.) the new ester polymerises in a short time (3-10 minutes), yielding a horny friable mass. Instead of hardened castor oil octadecyl glycollate or the methyl ester of a-hydroxy stearic acid or ll-hydroxy-stearic acid cetyl ester or the ricinoleic ester of stearic acid diglyceride may be used in a similar manner.

Example 2 A warm solution of '73 parts of castor oil in 230 parts of benzene is mixed with 18 parts of concentrated hydrochloric acid and 10 parts of nickel carbonyl, and the mixture is agitated with acetylene as described in Example 1. The whole is filtered to remove precipitated nickel chloride and heated for a further 2 hours at the boil while the water liberated during the reaction is separated with the aid of one of the known devices, and then the benzene is distilled off under reduced pressure.

78 parts of the triacrylic acid ester of castor oil remain behind in the form of an oil easily soluble in most solvents. The chief constituents of the new ester has the formula By heating it on the water-bath in the presence of a small quantity of benzoyl peroxide (for example, 0.1 per cent.) a horny solid polymerisate is obtained in a short time.

Emmple 3 A solution of 164 parts of commercial stearic acid diglyceride in 260 parts of benzene having a temperature of 50-60 C. is agitated with acetylene with the addition of 18 parts of concentrated hydrochloric acid (density=1.199) and 10 parts of nickel carbonyl. When the gas is no longer absorbed, the mixture is worked up as described in Example 2.

sesame.

5 'lfhererareobtained. 1.5.9.460: parts". oirthefacrylated dlglyceride: Off'the'j formula OCzH-s 2" (wherein.

is. the. acylradical. of commercialfstearic acid), whichisiastifiimass. after being cooled: It" melts easily when. heated. on the water-bath, and dissolves: welliin theusual solvents. Upon the addition. of. apsmall' quantity of; benzoyl. peroxide (for example,,0.1 percent) a viscous oil is gradually formed; which upongiurther heating /z-lv hour) isjconvertedinto a.slimy,.slightly gelatinous prodnot. At ordinary temperaturethe resulting polymerisate. is solid. and somewhat harder than the starting. material, but rather sparingly soluble in organic solvents.

Example 4 1154 parts of a diglyceride (molecular weight about 493) obtained by thereaction of commercial linseed oil with glycerine are dissolved in 175" parts of benzene and, after the addition of 18 parts of concentrated hydrochloric acid1(density=1.l99)- and loparts-of nickel carbonyl,.the solution having a temperature of 50.-60 C. is agitated'with acetylene until the gas is no longer absorbed.

After working up the productas described in Example 2 there are obtained 100 parts of an easily mobile oil, which after being heated on the water-bath for about 4-1 hour with the addition of a small quantity of benzoyl peroxide is converted into a soft, brittle, trituratable polymerisate. In a similar manner a diglyceride from henzoic acid; may be used as starting material.

Example 5 42 parts of commercial glycerine; mono-steerate are dissolved in. 135 parts of benzene having a temperature of 50 -60 C., and then mixed with 18. parts of concentrated hydrochloric acid (density=1L199) and parts of; nickel carbonyl and agitated with acetylene. When the absorption of the. gas has ceased, the whole is filtered, and the reaction solution is heated for 2 hours at the boil under reflux and while separating the water produced during the reaction. The solvent is then removed by distillation under reduced pressure leaving as a residue 42.5. parts of the acrylatedproduct. After cooling, the resulting monostearic acid diacryl'ic acid glyceride of the formula (wherein is the acyl radical of commercial stearic acid) is salve-like and easily soluble in most solvents. When heated for a short time on the water-bath after the addition of a small quantity of a polymerisation catalyst (for example,. 0.1 per cent ofbenzoyl'peroxide) the easily mobile oil changes into a stiff insoluble polymerisate. It can: be used for rendering textiles water repellent.

Example- 6 8-7- naltsg of; commercial 1 ricinoleie acidya ndi parts. of an; ordinarycommercialmixture-consisting predominantly:- of octadecyl. alcohol and; .a smaller. quantity of cetyl alcohol; are-heated in the-presenceof partsof. benzene and.5 -.5.par ts of: concentrated sulfuric acid (density=1.8l-), for d hoursatthe boil in areflux; apparatus, while the condensate-is allowedto return to the esteri fication vessel;v after passing through a waterremoving device.

The reaction product is. neutralised, with caleiunr carbonate and. a small. quantity: of... sodium carbonate solution, filtered whilewarm; and. used directly for acrylation.

One half of the solution of the ricinoleic acid ester prepared as described above, which contains about 100 parts of the ester, is heated to 50-60" C., then mixed with 18 parts of concentrated hydrochloric acid (density=l.199) and 10 parts of nickel carbonyl, and immediately agitated with acetylene. When the absorption of the gas has ceased, the filtered reaction product is heated under reflux for 2 hours, whilethe water split off during the'ester-ification is removed from the condensate returning to the esterification vessel by means of a water-removing device. Thesolvent is then removed by distillation under. reduced pressure. There remain as a residue 82.9.. parts of the new ester in the form of. apale-brown oil. It-consists of a-mixture of the ester of the formula and of the ester of the formula-- By heating the easily mobile. oilior about2-3 hours on the water-bath. in the presence of; a small quantity of benzoyl peroxide (for example, 0.1 percent) it is converted into a very viscous oil, which; is resinous after being cooled. The polymerisate dissolves fairly well inorganic solvents such as benzene, etc.

Example 7 A solution, heated to 40-50" C., of 80 parts of ricinoleic acid isopropyl ester (boiling at 206" C. under 5 mm. pressure) in 135 parts of benzene is mixed with 18 parts of concentrated hydrochloric acid (density=l.l99) and 10 parts of nickel carbonyl. The mixture is agitated-with acetylene until gasis no longer absorbed. After cooling the whole is filtered and further treated in the manner described in Example. 6.

The resulting O-acrylic acid ricinoleicacid isopropyl ester may be purifiedby distillationundier a high vacuum. In addition to an undistillable residue of apolymeric. product, it is obtained in a yield-of 65 per cent.,.and boils at l79-l87 C. under 0.1 mm. pressure.

The polymerisate is a viscous oil or a resin depending on the period of polymerisation.

Example 8 100 parts, of commercial sodium steal-ate are converted into the. ethylene glycol monostearic acid. ester by being heatedLwith. 100'parts of ethylene chlorhydrin and 83 parts of decalin with the addition of parts of sodium iodide.

When recrystallised from methanol and a small quantity of acetone, ethyl acetate or petroleum ether the ester melts at 63.5-64 C.

A warm mixture of 77 part of ethylene glycol monostearic acid ester in 175 parts of benzene is agitated with acetylene in the manner described in Example 1 with the addition of 18 parts of concentrated hydrochloric acid (density=1.l99) and 10 parts of nickel carbonyl until the gas is no longer absorbed. After working up in the manner described in Example 6, there are obtained 83 parts of stearic acid acrylic acid ethylene glycol ester of the formula is the acyl radical of commercial stearic acid.

The new ester is a salve-like mass and dissolves well in most solvents. By mixing the ester, liquefled by slightly heating it, With a small quantity of benzoyl peroxide (for example, 0.1 per cent.) it is converted after being heated for a short time (about 6-8 minutes) into a viscous oil, which after being further heated on the water bath 44 hours) forms a jelly. When cold the polymerisate is wax-like. When highly polymerised it is practically no longer soluble in any organic s01- vents and merely swells therein. Instead of ethylene glycol monostearic acid ester another ester of ethylene glycol, for instance, the lauric acid ester or the capric acid ester may be used. Moreover, in the above reaction the hydrochloric acid may be replaced by anhydrous acetic acid.

Example 9 92 parts of montanic acid (acid number=146.4, saponification number: 175.2, and ester number=28.8), are dissolved with heat in 50 parts of alcohol and 175 parts of benzene, and a warm solution of 9.6 parts of sodium hydroxide in 20 parts of water and 50 parts of alcohol is then added to the hot solution while stirring strongly.

The mixture which immediately becomes stiff is evaporated to drynessffinally at 100 C. under reduced pressure.

100 parts of sodium montanate are heated gradually to 120 C., while stirring, with 80 parts of ethylene chlorhydrin in 130 parts of decalin with the addition of 10 parts of sodium iodide. The whole is stirred for 16 hours at 120-125 C. The mass which is at first pasty becomes thinly fluid as sodium chloride separates. The reaction mixture is filtered while hot, residual sodium chloride is removed by washing with hot decalin, and the united solutions are freed from excess of glycol chlorhydrin and solvent by distillation. The re-' sidual' oil solidifies to a stifi mass after cooling. The yield amounts to 99-100 parts.

96 parts of the ethylene glycol monomontanic acid ester are dissolved in 265 parts of benzene with heat and, after the addition of 18 parts of concentrated hydrochloric acid (density=1.l99) and 10 parts of nickel carbonyl, agitated with acetylene in the manner described in Example 1 until gas is no longer absorbed. The whole is filtered hot to remove precipitated nickel chloride, and boiled for 2 hours under reflux as described in Example 6. The solvent is then removed by distillation under reduced pressure. After cooling, there are obtained 94 parts of a wax-like substance. The montanic acid acrylic acid glycol ester melts when moderately heated on the water bath and is easily converted into an infusible polymeric mass by the addition of a small quantity of benzoyl peroxide (for example, 0.1 per cent), which mass is no longer soluble in organic solvents.

Emample 10 60.5 parts of an ordinary commercial mixture consisting predominantly of octadecyl alcohol and a small quantity of cetyl alcohol (hydroxyl number=217 and saponification number=0) are dissolved in parts of benzene. 18 parts of concentrated hydrochloric acid (density=l.199) and 10 parts of nickel carbonyl are then added to the solution having a temperature of about 60 C.

The warm mixture is agitated with acetylene as described in Example 1 until gas is no longer absorbed. After cooling, the solid precipitated nickel chloride is removed by filtration and the solution is heated for 2 hours under reflux and with removal of the water liberated during the reaction, whereby the small quantity of free acrylic acid formed as a by-product is also esterified. The solvent is then removed by distillation under reduced pressure, and the residual oil may be distilled under a high vacuum. After separating a small amount of material which distils initially, the new acrylic acid ester, a mixture of distils under 0.1 mm. pressure at -169 C. and is a colorless mass after being cooled. The yield amounts to 51 parts.

Example 11 70 parts of commercial ricinoleic acid are dissolved in 135 parts of benzene heated at 50-60 C., then mixed with 18 parts of concentrated hydrochloric acid (density=l.l99) and 10 parts of nicke1 carbonyl, and at the same time agitated with acetylene until gas is no longer absorbed. The cooled reaction liquid is filtered and then the acrylic acid formed as a by-product is esterified by boiling the reaction liquid for 2 hours under reflux while removing water.

After removing the benzene by distillation under reduced pressure there are obtained 77 parts of a pale brown oil which is gradually converted into a viscous oil by heating it on the water bath in the presence of a polymerisation catalyst. The polymerisate still dissolves quite well in organic solvents, for example benzene. The chief constituent of the monomer corresponds to the formula A mixture, heated at about 40 C., of 90 parts of dodecylalcohol (boiling at 142-l47 C. under 13 mm. pressure), 36 parts of concentrated hydrochloric acid (density=l.199) and 20 parts of nickel carbonyl is agitated with acetylene under assasi se arated and the @c ude ester .is e eated y Washed water and 1anormalsoluiion-of sod um bicarbonate- 'Ino de toatta n.a-be te i enaration it is recommended after the treatment with the alkaline washing liquid, to add petroleum ether, a small quantity of concentrated sodium chloride solution and a very small quantity of phosphoric acid.

The crude ester is obtained, after drying with sodium sulfate and distilling off any added solvent under reduced pressure, in a yield of 106.5 parts.

For further purification the product may be fractionally distilled under a high vacuum. The pure ester of the formula CHFCHC O-GmHn boils at 121-138 C. under 0.07-0.15 mm. pressure. Instead of hydrochloric acid anhydrous acetic acid may be used.

Example 13 (a) 2 parts of the acrylic acid montanic acid ethylene glycol ester described in Example 9 are mixed with 2 parts of the acrylic acid distearic acid glycerine ester described in Example 3 with heat and occasional stirring and heated, after the addition of 0.04 part of benzoyl peroxide, at 95-100 C. until the oil begins to become thickly liquid (about 3-9 minutes).

The resulting polymerisate is immediately dissolved in 40 parts of benzene, and a fibrous material, for example, a cotton fabric is impregnated with the solution. The product remaining on the fiber after evaporation of the solvent is afterpolymerised by heating the treated material for 1 hour, whereby a water-repellent dressing is produced which is substantially unaffected by washing with aqueous baths and by treatment with organic solvents. Furthermore, the fabric finished in this manner has a soft full feel.

(b) A mixture of 5 parts of acrylic acid stearic acid ethylene glycol ester described in Example 8 and 5 parts of the triacrylic acid ester of hardened castor oil described in Example 1 is mixed while stirring and heating on the water bath with 0.1 part of benzoyl peroxide, which is advantageously added in solution in a small quantity of benzene. The resulting oil is then dissolved in 100 parts of benzene and a fibrous material, for example, cotton gaberdine or poplin, is then impregnated with the solution. After squeezing the material and evaporating the solvent, the material is heated for one hour at 120 0., whereby the substance is polymerised on the fiber and rendered insoluble.

The fabric so treated has a water-repellent finish similar to that of the material treated as described under (a) above.

Having thus described the invention, what is claimed is:

1. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of a hydroxy compound which contains at least one alcoholic hydroxy group and at least 10 one:carbon-chainmithat least .12LCfirhmlratOm intneipresence ofwaterand of: wat nzins uble or anic solvent .sel cted'from th roup onsistr ing. ofhydrpcarbons of theben ene-series. hydro? carbons 0f .the b nzine series and -mixtur es thereof.

.A process fQr-themanufaciureof .amaurlic acid st which compr ses t ea in a etylene with nickelicarbonyl-with the addition of an acid andofdodecyl:alcohol, in the presence of water and of a water-insoluble organic solvent selected from the groupconsis'ting of hydrocarbons of the ben en -ser es yd oca b n 9 th benzine serie and mixtures thereof."

3. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of aqueous hydrochloric acid, of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof and of dodecyl alcohol under an acetylene pressure which exceeds one atmosphere.

4. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of a partial ester of a polyhydric alcohol with an aliphatic carboxylic acid containing at least 12 carbon atoms, in the presence of water and of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof.

5. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of glycerine-monostearate, in the presence of water and of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof.

6. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of stearic acid-fi-hydroxyethyl ester, in the presence of water and of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof.

7. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of an ester of an aliphatic hydroxycarboxylic acid containing 18 carbon atoms, in the presence of Water and of a water-insoluble organic solvent 1 selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof.

8. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of castor oil, in the presence of water and of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof.

9. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of an ester of hardened ricinoleic acid, in the presence of water and of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydro carbons of the benzine series and mixtures thereof.

10. A process for the manufacture of an acrylic acid ester which comprises treating acetylene with nickel carbonyl with the addition of an acid and of hardened castor oil in the presence of water and of a water-insoluble organic solvent selected from the group consisting of hydrocarbons of the benzene series, hydrocarbons of the benzine series and mixtures thereof.

OTTO ALBRECHT. ARTHUR MAE-DER.

REFERENCES CITED The following references are of record in the file of this patent:

12 UNITED STATES PATENTS Number Name Date 2,141,546 Strain Dec. 27, 1938 OTHER REFERENCES Modern Plastics, November 1945, pages 162, 163 and 210.

Reppe: Advances in Acetylene Chemistry, Enemy Technical Information, Intelligence Div.

10 Report No. 4149, February 12, 1946, pages 21-23. 

1. A PROCESS FOR THE MANUFACTURE OF AN ACRYLIC ACID ESTER WHICH COMPRISES TREATING ACETYLENE WITH NICKEL CARBONYL WITH THE ADDITION OF AN ACID AND OF A HYDROXY COMPOUND WHICH CONTAINS AT LEAST ONE ALCOHOLIC HYDROXY GROUP AND AT LEAST ONE CARBON CHAIN WITH AT LEAST 12 CARBON ATOMS, IN THE PRESENCE OF WATER AND OF A WATER-INSOLUBLE ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF HYDROCARBONS OF THE BENZENE SERIES, HYDROCARBONS OF THE BENZINE SERIES AND MIXTURES THEREOF. 